Vat dyestuffs of the pyrazolanthrone series and process of making them



Patented Aug. 1, 1933 tree sr use aren't. oFFIcE VAT DYESTUFFS or THE -PYRAZOLAN- 'rnaona seams AND PROCESS or MAKING THEE I Paul Nawiasky and Artur Krause, Ludwigshafen-on-the-Rhine, Germany, assigners to General Aniline Works; 1110., New York, N. a Corporation of Delaware No Drawing. Original application DecemberlZl,

1926, Serial No.. 156,256.

Divided and this application November 25, 1927, Serial No. 235,750, and in Germany December 22, 1925 .8. Clainis. .(C 1 260-45) This application for patent isfor subject matter which asmeen removearmm the application for patent Ser. "No; 156,256 filed Describedfor converting the saidfpyrazolanthrones employed for the'process of the, German Patent No; 255,641 into allrylation'products."

We have now found that these alkylationprodilcts are converted into vat dyestuifs dyeing from,

yellow to red shades .by treatment. with alkaline condensing "agents.

The treatment of the said alkylation products withijallralin e condensing agents may be 'carried out inany known or suitable manner. For example it "may he eifectedbyheating with alcoholic caustic potash. Another very suitable method is the treatment" with metal arylides in theUQ S. application for patent by'Arthur Luettringhaus and Hugo -Wo1fi for an improve ment in the productionof isodibenzanthrones, Ser. No. 62,933, filed October 16th, 1925,. matured into U. S. Patent No. 1,725,590. 1

The dyestuffs obtained from alkylene-dhpyerazolanthrones dye from yellow to orange shades,

while those obtained from alkyhpyrazolain thrones produce more or less red dyeings.

40 The following examplesfurther illustrate how the invention may be. carried out in practice, but

the invention is not restricted thereto. The'parts are by weight; f, p

' Y Emample'l" eral hours with 1 part of sodium carbonate and .1 part of the methyl ester of toluene sulfonic acid, in 30 parts oi trichlorbenzene, whereupon the latter vis expelledby steam distillation, "25

In the parent applicationa process is de-, 9, bluevat.

suchas sodium anilide in the manner described.

1 part of pyrazolanthrone is heated for sev-..

parts of the product thus obtained or more. suit ably of that obtainable in accordance with Example 3 of theparent specification are introduced 7 into 'a melt 'of alcoholic potash prepared by heating 12.5 parts of caustic potash with 10' parts of ethyl alc oholat 120 C. The mixture isl'stirred for hour and a half i at 120 0., and the meltis then poured into a large quantity of water. The dyest ufi is precipitated by blowing air through the liquid, filtered'ofi by suction, washed with Water, dried, and freed-from impurities by boiling with alcohol. The resulting dyestuff isfa red powder, which dissolves to an orange-colored solution in concentrated "sulfuric acid, and producesblue dyeings on cotton from I On exposure to the air the color changes, by oxidation, to ared having a very ably corresponds to one of the following formu V V Similar dyestuffs are "obtainedby I using the bluish tinge. The 'dyestuff' 'thusjobtained prob} product resulting from the'actionof 'the ethyl U ester of toluene sulfonic acid on pyrazolanthrone, or the product of the reaction of alkylating" agentswon nuclear-substitu ted pyrazolanthrones. l

Example 2 The sodium compound of pyrazolanthron e is condensed with methylene chlorid by heating uwith an excess of the latter at 140. to 150 C.

in an autoclave. The condensation product when crystallized from dichlorbenzene melts at, 350- to 355 C. and has the composition as determined by analysis 1 I 1 l0 partsthereof are introduced at 1 1 5 :to 120 .0. into a melt of 100 parts of caustic potash and 100 parts of ethyl alcohol.

7 t The said'temperatu'reis maintainedfor a short time until the formation of the dyestuff iscomplete; the melt a red coloration.

It dyes cotton from a warm blue vat blue shades which bythe oxidizing action of the air turn to a pure yellow. The dyeings thus produced are very fast to chlorine and bucking. The dye stuff dissolves in concentrated sulfuric acid with c When employing as condensing agent a suspension of sodium anilide in aniline, the dyestuff is formed at a considerably lower temperature, for example at 30 C. In this case the a product may'be worked up for example by dis solving the aniline by treatment with dilute acid and separating the coloring matter from by products by treatment with suitable solvents for example with ethyl alcohol.

Etcample 3 g A condensation product of ethylene bromide Y and the sodium compound of pyrazolanthrone may be obtained by heating the said sodium compound for example with twice its weight of ethylene bromide to 140.130 150 C. When crystallized from trichlorbenzene it melts at 364 to 368 C. 1 0 parts thereof are introduced into a melt consisting of 100 parts of caustic potash and 100 parts :of ethyl alcohol and heated to 120th 130 C. The said temperature isv maintained forabout half an hour until the formation of the dy'e'stuif is completed, and the product is worked up as described 'inExample l. The reaction probably proceeds according to one of the following-schemesr- The new dyestufi dyes cotton from a warm blue vat blue shades; when exposed to the air the dyeings are converted into a very fast orange,

N n olnelfe-l f The dyestuif dissolves in concentrated sulfuric acid with a red coloration.

The same coloring matter is obtained by heating pyrazolanthrone with ethylene glycol ditoluene sulfonic acid ester and sodium carbonate less 211 in tri'chlorbenzene and acting on the product so obtained as described above with a melt of alcoholic caustic potash. When employing instead of the said condensation product that obtainable from the sodium compound of pyrazolanthrone and 1.2-dibrom-propane, a vat dyestuff producing orange shades is obtained which is onlylittle different in its properties from that described above. v

We claim: I

1. As new articles of manufacture vat dyestuffs of the pyrazolanthrone series producing yellow to orange dyeings, which dyestuifs are obtainable by the action of an alkaline condensing agent on I an alkylene-di-pyrazolanthrone,in which the alkylene radicle contains" more than one carbon atom.

2. As a new article of manufacture, a vat dye-,

stufi of the pyrazolanthrone series, which dyes cotton from a blue vat blue shades turning to a very fast orange on oxidation and dissolves in concentrated sulfuric acid with a red coloration,

and whichis obtainable by the action of an alkaline condensing agent on ethylene-di-pyrazolanthrone.

tained by treating a .pyrazolant'hrone in the .pres- D80 less 2H less 2H ence of an acid condensing agent with an *etlkyl ester of an aryl-sulphonic acid.

4. The process of producing yellow to red vat dyestuffs of the pyrazolanthrone series which comprises acting with an alkaline condensing agent on a compound selected from the group consisting of those alkylene dipyrazolanthrones in which the alkylene group containsup to three carbon atoms, and those alkyl-pyrazolanthrones which can be obtained by treating a pyrazolanthrone in the presence of an acid condensing agent with an alkyl ester of an aryl, sulphonic acid in which the alkyl group contains up to three carbon atoms. V

6. The process of producing yellow to red vat dyestufis'of the pyrazolanthrone series which comprises acting with an alkaline condensing agent on the methyl-pyrazolanthrone which can be obtained by treating pyrazolanthrone in the presence of an acid condensing agent with a methyl ester of an aryl sulphonic acid. '7. The process of producing yellow to red vat dyestuffs of the pyrazolanthrone series which:

comprises acting with an alkaline condensing agent on methylene-dipyrazolanthrone. V

'8. The process ofproducing yellow to red vat dyestuffs of the pyrazolanthrone series which comprises acting with an alkaline condensing agent on ethylene-dipyrazolanthrone.

PAUL NAWIASKY. m'ron KRA sE, 

